Derivatives of benzobistriazoles



United States Patent 3,18,796 DERIVATIVES 0F BENZOBISTRIAZGLES William Lindsay Mosby, North Plainfield, and Mary- Louise ilva, Somerville, N.J., assignors to American Cyanamid Company, Stamford, Conn-., a corporation of Maine No-Drawing. Filed 'Aug. 21, 1963, Ser. No. 303,659 4 Claims. (Cl. 260-2475) This invention relates to, and has for its object, the provision of new compounds and the process for preparing said compounds.

More particularly, it relates to the product bis-(aminotriazolo)-p-quinone of the Formula I:

wherein R, R and R are individually either lower alkyl, phenyl, halophenyl, lower alkylphenyl, lower alkoxyphenyl, di-lower alkylamino, naphthyl, morpholino, pyr-rolidino, piperidino or piperazino. This may be accomplished by treating the compound of Formula II with an aqueous strong acid (e.g., hydrochloric, sulfuric, nitric, phosphoric and toluenesulfonic acids) at elevated temperatures (for example, between 50 C. and reflux) employing a solvent (e.g., acetic acid, ethanol, methoxyethanol and ethyleneglycol). The product, obtained as a colored precipitate, may be separated by filtration and purified by conventional crystallization techniques.

The starting materials for the preparation of I are themselves new compounds. They are obtained from the reaction of 2,3,5,6-tetrazido-p-quinone with two moles of a phosphine or phosphorous t-riamide of the Formula III:

wherein R, R and R are as defined above.

The reaction is carried out in an inert solvent such as toluene, methylene chloride, ethyl acetate, ethylene chloride, benzene, chloroform, chlorobenzene, diethyl ether, dibutyl ether, carbon tetrachloride, nitromethane, etc. The reaction temperature may be between 20 and 200 C. The desired material may be separated .from the reaction mixture by filtration or by evaporation of the solvent and (III) 3,198,796 Patented Aug. 3, 1965 then purified :by conventional recrystallization techniques.

Among the alkyl phosphines which may be employed are the lower alkyl phosphines such as trimethylphosphine, triethylphosphine and tributylphosphine.

Among the triaryl phosphines which can be used are tri-phenylphosphine, the tritolylphosphines, such as tri-otolylphosphine, the chlorophenylphosphines, such as tris- (4-chlorophenyl)phosphine, the lower alkoxyphenylphosphine-s, such as tris(2-methoxyphenyl)phosphine, trinaphthylphosphines, and also mixed triaryl phosphines, such as di-phenyl-p-tolylphosphine, diphenyl-4-meth'oxyphenylphosphine, diphenyl-4-chlorophenylphosphine, phenyl-bisp-tolylphosphine, 4-.chlorophenyl-bis-p-tolylphosphine.

The phosphorous triamides which may be used include phosphorous tripiperidide, phosphorous trimorpholide, N,N,N',N,N",-N"-hexaethylphosphorous triamide, N,N, N',N',N"N"-hexaisopropylphosphorous triamide.

The following examples in which parts are by weight are presented to illustrate the present invention.

EXAMPLE 1' N,N' *(4,8-dihydro-4,8-diox0-2H,6H-benz0[1,2-d;4,5-d']' bis-triazole-2,6-diyl) bis(P,P,P-triphenylphosphine imide) about parts of methylene chloride, and the solution was dried over anhydrous magnesium sulfate. To the above solution of 2,3,5 ,6-tetrazidobenzoquinone there was slowly added 5.24 parts of triphenylphosphine at ambient,

temperature. The solution was concentrated .by evaporating part of the solvent in vacuo. The precipitate was separated, wa-shed with methyl cyclohexane and boiling nit-r0- methane and recrystallized from chlorobenzene. The Orange product became black at a temperature above 300 C., but remained unmelted at 360 C.

EXAMPLE 2 Foamy This product is prepared by reacting tetrazidobenzoquinone with trirnorpholinophosphine in accordance with the procedure of Example l.

. (3 This product is obtained .by reacting tetrazidobenzoquinone with .tris-(3,4,5-trimethoxyphenyl)phosphine in accordance with the procedure of Example 1.

EXAMPLE 4 EXAMPLE 5 0 r N H N CH3 CH3 N P=NN/ \NN=P(N CH: 3 CH3 3 N H N s This product is obtained by reacting tris-dimethylaminophosphine and tetrazidobenzoquinone in accordance with the procedure of Example 1.

N/ n N 0 A suspension of 0.45 part of the product of Example 1 in 3 parts of glacial acetic acid plus about one part of concentrated hydrochloric acid was boiled for one minute. About one pant of water was added slowly while boiling was-continued. After cooling, the precipitate was separated by filt-ration and washed with methyl alcohol and petroleum ether. -fron1 glycol diacetate, became iblack at a temperature above 300 C., but remained unmelted at 360 C,

The product, after recrystallization The identical product is obtained when the products of Examples 2-5, respectively, are substituted for the product of Example 1 in the foregoing procedure.

We claim: -1. The compound of the formula:

wherein R, R and R are individually selected from the group consisting of lower alkyl, phenyl, halophenyl, lower alkylphenyl, lower alkoxyphenyl, di-lower alkylamino, naphthyl, morpholino, pyrrolidino, piperidino and piperazino.

3. A process which comprises treating a compound of claim 2 with an aqueous strong acid at a temperature between C. and reflux in the presence of a water miscible solvent, and recovering the product of the formula:

4. The process of claim 3 wherein the acid is a member selected from the group consisting of hydrochloric, sul- =furic, nitric, phosphoric and toluene-sulfonic.

No references cited.

NICHOLAS S, RIZZO, Primary Examiner. 

1. THE COMPOUND OF THE FORMULA:
 2. THE COMPOUND OF THE FORMULA:
 3. A PROCESS WHICH COMPRISES TREATING A COMPOUND OF CLAIM 2 WITH AN AQUEOUS STRONG ACID AT A TEMPERATURE BETWEEN 50*C. AND REFLUX IN THE PRESENCE OF A WATER MISCIBLE SOLVENT, AND RECOVERING THE PRODUCT OF THE FORMULA: 2,6-DI(H2N-)-4,8-DIHYDROBENZO(1,2-D:4,5-D'')BISTRIAZOL4,8-DIONE 